EP1565591A2 - Method for vapor-depositing strip-shaped substrates with a transparent barrier layer made of aluminum oxide - Google Patents

Method for vapor-depositing strip-shaped substrates with a transparent barrier layer made of aluminum oxide

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Publication number
EP1565591A2
EP1565591A2 EP03757995A EP03757995A EP1565591A2 EP 1565591 A2 EP1565591 A2 EP 1565591A2 EP 03757995 A EP03757995 A EP 03757995A EP 03757995 A EP03757995 A EP 03757995A EP 1565591 A2 EP1565591 A2 EP 1565591A2
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EP
European Patent Office
Prior art keywords
aluminum
reactive gas
layer
barrier layer
vapor
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EP03757995A
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German (de)
French (fr)
Other versions
EP1565591B1 (en
Inventor
Nicolas Schiller
Steffen Straach
Mathias Raebisch
Matthias Fahland
Christoph Charton
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/027—Graded interfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium

Definitions

  • the invention relates to a method for evaporating a barrier layer made of aluminum oxide onto band-shaped substrates in a vacuum.
  • the coating of preferably tape-shaped substrates with a barrier layer is an important process step in the production of various packaging materials.
  • a thin metal layer e.g. aluminum
  • polymer materials in particular are further processed into packaging materials that have a high barrier effect against oxygen and water vapor, possibly also against aroma substances.
  • Packages that contain a thin metal layer are opaque and have a high microwave absorption. This is disadvantageous for some applications in the field of food packaging. For this reason, metallic barrier layers are increasingly being replaced by various oxide-based barrier layers (oxides of Si, Al, Mg).
  • the reactive evaporation of aluminum from the boat evaporator represents a possibility to combine the advantage of a low evaporation temperature with a high optical transparency and good microwave permeability of the end product.
  • methods using electron beam or induction evaporators are also possible.
  • the optical transmission depends on the mixing ratio between aluminum and its oxide - hereinafter also referred to as stoichiometry. As the proportion of oxide increases, the optical transmission increases while the barrier effect of the layer is reduced.
  • barrier layers which as individual layers do not meet the minimum requirements with regard to their barrier effect, show sufficient barrier effects in multilayer systems.
  • the combination of sputtered and evaporated layers is such a solution that has also been proposed for aluminum oxide (DE 43 43 040 C1).
  • the coating takes place at a very different coating rate.
  • the implementation of several successive process steps, which require different throughput times also represents a considerable additional technical outlay.
  • the barrier effect of such layers is often limited by the fact that different layer tensions build up in the individual layers, which is why, starting from the transition areas, it gradually increases Cracks can form.
  • the object of the invention is to provide a method with which transparent barrier layers based on aluminum oxide can be produced by reactive evaporation on tape-shaped substrates without great technological effort.
  • the work area determined by the required transmission and barrier values should be maintained without additional post-oxidation.
  • the process should also be able to be carried out by retrofitting existing aluminum vapor deposition systems.
  • the invention is based on the knowledge that the barrier effect of an aluminum oxide layer is significantly less stoichiometry-dependent if the substrate is provided with an extremely thin sputtered metal or metal oxide layer before the aluminum oxide layer is deposited.
  • Extremely thin is understood to mean a layer thickness at which a closed layer cannot yet form. This can be ruled out in any case if the area coverage is not sufficient for the formation of a complete atomic or molecular layer, but somewhat higher area coverage does not yet lead to the formation of closed layers.
  • the sputtering process also called sputtering, requires cleaning and activation of the substrate surface. This increases shift liability.
  • the metal atoms or metal oxide molecules sputtered on at the same time have particularly good adhesion due to the impact energy typical of sputtering processes, as is also known from thicker sputtered layers. It is advantageous however, that due to the incomplete covering of the substrate with an unclosed layer, no layer tensions build up.
  • the substrate areas not yet covered after sputtering are also activated and cleaned for coating with the actual barrier layer made of aluminum oxide. It was found that the dependence of the barrier effect on the layer stoichiometry is much less pronounced with such a precoating than without this precoating.
  • barrier effects can be achieved if a plasma-activated reactive vapor deposition of the pre-coated substrate with aluminum oxide then takes place.
  • a dense hollow cathode arc discharge plasma is particularly suitable for plasma activation. Its effect can be further increased by magnetic amplification. This requires a particularly low dependence of the barrier effect on the layer stoichiometry with consistently good barrier values.
  • this special plasma due to its high charge carrier density, leads to the formation of an optimal layer structure for barrier layers.
  • a plasma has proven to be advantageous which provides an average extractable ion current density of at least 20 mA / cm 2 on the substrate. Ion current densities of over 50 mA / cm 2 are particularly advantageous.
  • a particularly advantageous embodiment of the method according to the invention results from the fact that the barrier to oxygen does not depend on the stoichiometry in the same way as the barrier to water vapor.
  • the degree to which certain depth regions of the layer contribute to the barrier effect of the overall layer depends to a different degree on the stoichiometry. If the optical transmission of the entire layer is kept constant in accordance with the later application-related requirements, the absorption of the different depth ranges of the layer can certainly vary.
  • a layer with stoichiometry evenly distributed over the entire layer thickness cannot be distinguished from a stack structure of completely transparent and more sub-stoichiometric partial layers. The same applies to layers which are designed as gradient layers with respect to the stoichiometry. Different gradients cannot be seen from the measurement of the optical transmission as long as the absorption of the entire layer does not change.
  • barrier layers with an excellent barrier effect can be produced. It is particularly advantageous that both coating steps can be carried out with the same throughput time of the substrate, since the coating rates move in a similar relationship to one another as the area occupancies through the non-closed sputter layer and the actual barrier layer. Coating can thus be carried out in a single pass.
  • the method according to the invention consists in the precoating of the substrate by reactive or non-reactive sputtering with a non-closed layer made of a metal or its oxide and a subsequent reactive evaporation of aluminum from a boat evaporator, an induction evaporator or an electron beam evaporator.
  • the step of reactive vapor deposition is advantageously supplemented by plasma activation and the reactive gas is let in in such a way that a suitable partial pressure gradient of the reactive gas is established along the vapor deposition zone in the direction of strip travel.
  • aluminum oxide layers can thus be vapor-deposited onto band-shaped substrates which, with regard to their stoichiometry or the mixing ratio between the evaporated metal and its oxide, are designed as gradient layers or as stacked layers and whose most sub-stoichiometric region lies in the part of the layer close to the substrate.
  • gradient layers have the advantage over stacked structures that they can be vapor-deposited in one process step.
  • the depth range of the layer absorbing in the visible range can be kept very thin, ie at ⁇ 10 nm. Since fluctuations in the degree of sub-stoichiometry on such thin layers only become apparent when there are clear deviations, and changes in super-stoichiometric areas - as long as they remain super-stoichiometric or at least stoichiometric - have no influence on the absorption of the overall layer the requirements for maintaining a just tolerable absorption are much less critical than is the case with layers with essentially uniform stoichiometry.
  • the reactive evaporation can also be plasma-activated in the case of the formation of gradient layers, which further improves the barrier properties of the end product.
  • the main advantage of the method, including gradient layers is the extremely small thickness of the substoichiometric layer, which means that a significant transmission loss only occurs when the degree of oxidation is very low. In most cases, this means that an additional post-oxidation step is unnecessary. All other layer areas are transparent anyway. In this case, the method therefore does not aim to achieve the weakest but very uniform sub-stoichiometry, but rather the creation of a gradient layer which has a very thin but definitely more sub-stoichiometric zone in its lower region. This makes it much easier to meet the uniformity requirement with regard to optical transmission.
  • the use of the hollow cathode arc discharge plasma according to the invention additionally reduces the dependency of the barrier properties on the stoichiometry of the oxide layer and thus expands the available work area.
  • Process reliability is particularly high if process parameters are regulated. It is particularly advantageous if the respective process parameters are regulated separately for individual sectors of the vapor deposition area. Suitable process parameters to be controlled are the amount of aluminum evaporated per unit of time and / or the reactive gas flow. It is particularly advantageous if the regulation is a transmission-controlled regulation of the oxygen supply, in which the oxygen supply is adjusted in such a way that the optical transmission, which is measured continuously or periodically during the process, is kept at a desired value.
  • a particularly advantageous embodiment of the method consists in arranging a movable diaphragm to limit the vaporization area. This means that in the event that for structural reasons - e.g. B. in the lower part of the layer - do not let superstoichiometric areas be avoided, hide them.
  • the substrate to be vaporized - in this case a PET film - is guided past a magnetron source covered with titanium targets, which serves as a sputtering source while admitting argon and oxygen.
  • a magnetron source covered with titanium targets which serves as a sputtering source while admitting argon and oxygen.
  • Single or double arrangements of magnetrons are used as the magnetron source.
  • the power fed in is adjusted in such a way that an unclosed layer forms on the substrate.
  • the area coverage is less than an effective layer thickness of one nanometer.
  • the optimal sputtering performance depends on the realized belt speed.
  • the substrate is then passed over a chill roll.
  • evaporation material in evaporator boats which is continuously fed to the evaporator boats in a known manner and is evaporated onto the substrate.
  • the evaporator boat is operated at a constant evaporation rate.
  • the effective steaming range can be set using a movable screen.
  • Gas inlet nozzles for supplying the reactive gas oxygen are arranged to the side of the vaporization area between the cooling roller and the evaporator boat. The positions of the gas inlet nozzles and their angles can be adjusted in the direction of the arrow.
  • the reactive gas flow through the gas inlet nozzles near the strip inlet zone can be adjusted manually.
  • the reactive gas flow through the other gas inlet nozzles is transmission-controlled.
  • the measurement of the optical transmission required for this is carried out by means of known measuring devices outside the vapor deposition zone, but before reaching the winding.
  • the aluminum evaporation is started up in a known manner.
  • the reactive gas flow at the gas inlet nozzles in the vicinity of the strip inlet zone is then adjusted to 0 to 40% of the amount of oxygen required for a complete oxidation of the entire layer in accordance with the chemical reaction equation.
  • the regulated gas inlet nozzles on the strip outlet side are then opened, specifying the desired setpoint for the optical transmission of 80 to 95%, whereupon the reactive gas flow that is still required is automatically set.
  • the reactive gas flow to be set at the gas inlet nozzles must be determined as follows:
  • the substrate is vapor-deposited at various settings of the reactive gas flow at the gas inlet nozzles.
  • the vaporized substrates are then measured for their permeation values for water vapor and / or oxygen.
  • the reactive gas flow, at which the lowest permeation value for water vapor and / or oxygen resulted, is then set at the gas inlet nozzles.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)
  • Inorganic Insulating Materials (AREA)
  • Chemical Vapour Deposition (AREA)
  • Chemically Coating (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The invention relates to a method for vapor-depositing strip-shaped substrates with a transparent barrier layer made of aluminum oxide by reactively vaporizing aluminum and admitting reactive gas in a strip vapor-deposition installation. The invention provides that, before coating with aluminum oxide, a partially enclosed layer made of a metal or of a metal oxide is applied to the substrate by magnetron sputtering.

Description

Verfahren zum Bedampfen bandförmiger Substrate mit einer transparenten Barriereschicht aus AluminiumoxidProcess for the vapor deposition of ribbon-shaped substrates with a transparent barrier layer made of aluminum oxide
Die Erfindung betrifft ein Verfahren zum Aufdampfen einer Barriereschicht aus Aluminium- oxid auf bandförmige Substrate im Vakuum.The invention relates to a method for evaporating a barrier layer made of aluminum oxide onto band-shaped substrates in a vacuum.
Die Beschichtung vorzugsweise bandförmiger Substrate mit einer Barriereschicht ist ein wichtiger Prozessschritt bei der Herstellung von verschiedenen Verpackungsmaterialien. Insbesondere Polymermaterialien werden nach Aufdampfen einer dünnen Metallschicht (z. B. Aluminium) zu Verpackungsmaterialien weiterverarbeitet, die eine hohe Sperrwirkung gegenüber Sauerstoff und Wasserdampf, evtl. auch gegenüber Aromastoffen, aufweisen. Verpackungen, die eine dünne Metallschicht enthalten, sind undurchsichtig und haben eine hohe Mikrowellenabsorption. Das ist für manche Anwendungen im Bereich der Lebensmittelverpackungen von Nachteil. Deshalb werden zunehmend metallische Barriereschichten durch verschiedene Barriereschichten auf Oxidbasis (Oxide von Si, AI, Mg) ersetzt.The coating of preferably tape-shaped substrates with a barrier layer is an important process step in the production of various packaging materials. After vapor deposition of a thin metal layer (e.g. aluminum), polymer materials in particular are further processed into packaging materials that have a high barrier effect against oxygen and water vapor, possibly also against aroma substances. Packages that contain a thin metal layer are opaque and have a high microwave absorption. This is disadvantageous for some applications in the field of food packaging. For this reason, metallic barrier layers are increasingly being replaced by various oxide-based barrier layers (oxides of Si, Al, Mg).
Die reaktive Verdampfung von Aluminium aus dem Schiffchenverdampfer stellt dabei eine Möglichkeit dar, den Vorteil einer niedrigen Verdampfungstemperatur mit einer hohen optischen Transparenz und guter Mikrowellendurchlässigkeit des Endproduktes zu kombinieren. Daneben kommen jedoch auch Verfahren mit Elektronenstrahl- bzw. Induktionsverdampfern in Frage.The reactive evaporation of aluminum from the boat evaporator represents a possibility to combine the advantage of a low evaporation temperature with a high optical transparency and good microwave permeability of the end product. In addition, however, methods using electron beam or induction evaporators are also possible.
Für Barrierebeschichtungen dieser Art gilt, dass die optische Transmission vom Mischungsverhältnis zwischen Aluminium und seinem Oxid - im Folgenden auch als Stöchiometrie bezeichnet - abhängt. Mit steigendem Oxidanteil nimmt die optische Transmission zu, während sich damit jedoch die Barrierewirkung der Schicht verringert. Es existiert ein Arbeitsbereich im leicht unterstöchiometrischen Bereich, dessen untere Grenze durch die höchstzulässige Absorption und dessen obere Grenze durch die geforderten Mindestwerte der Barriere bestimmt wird [Schiller, N.; Reschke, J.; Goedicke, K.; Neumann, M.: Surface and Coatings Technology, 86-87 (1996) 776-782]. Es ist deshalb üblich, die Einhaltung dieses Arbeitsbereiches durch Bereitstellung der Reaktionspartner Aluminium und Sauerstoff in einem bestimmten einstellbaren Mengenverhältnis zu gewährleisten (JP 62-103 359 A).For barrier coatings of this type, the optical transmission depends on the mixing ratio between aluminum and its oxide - hereinafter also referred to as stoichiometry. As the proportion of oxide increases, the optical transmission increases while the barrier effect of the layer is reduced. There is a work area in the slightly substoichiometric range, the lower limit of which is determined by the maximum permissible absorption and the upper limit of which is determined by the required minimum values of the barrier [Schiller, N .; Reschke, J .; Goedicke, K .; Neumann, M .: Surface and Coatings Technology, 86-87 (1996) 776-782]. It is therefore customary to ensure that this working range is maintained by providing the reactants aluminum and oxygen in a certain adjustable ratio (JP 62-103 359 A).
Da gerade auf dem Gebiet von Massenverpackungen die visuelle Beurteilung des fertigen Produkts eine große Rolle spielt und geringe Schwankungen der Transmission sehr schnell wahrgenommen werden können, wurden bereits zahlreiche Versuche unternommen, eine gleichmäßige Transmission über große Beschichtungsflächen zu erzielen, wobei neben der Transmission stets auch eine ausreichende Schichthaftung angestrebt werden musste, um eine Barrierewirkung zu erzielen.Since the visual assessment of the finished product plays a major role in the field of bulk packaging and small fluctuations in transmission can be perceived very quickly, numerous attempts have already been made to achieve uniform transmission over large coating areas, with the addition of Transmission always had to strive for sufficient layer adhesion in order to achieve a barrier effect.
Es ist bekannt, dass durch die Messung der optischen Transmission der reaktiv aufgedampf- ten Schichten die Steuerung des Prozesses möglich ist, indem bei vorgegebenem Gasstrom die Verdampfungsrate so nachgeführt wird, dass ein vorgegebener Transmissionswert eingehalten wird. Das ist bei der reaktiven Elektronenstrahlverdampfung realisiert (DE 44 27 581 A1). Mit einem Schiffchenverdampfer ist diese Form der Regelung nicht durchführbar, da die Verdampferschiffchen für schnelle Änderungen des Heizstromes - und damit der Verdampfungsrate - ungeeignet und für eine derartige Regelung zu träge sind.It is known that the measurement of the optical transmission of the reactively vapor-deposited layers makes it possible to control the process by tracking the evaporation rate for a given gas flow in such a way that a given transmission value is maintained. This is achieved with reactive electron beam evaporation (DE 44 27 581 A1). This type of control cannot be carried out with a boat evaporator, since the evaporator boats are unsuitable for rapid changes in the heating current - and thus the evaporation rate - and are too sluggish for such a control.
Es ist weiterhin bekannt, dass durch die Einstellung eines bestimmten Reaktivgasflusses, der bei konstanter Verdampfungsrate zu schwach absorbierenden Schichten führt, das Mischungsverhältnis zwischen dem verdampften Metall und seinem Oxid im Wesentlichen gleichförmig gehalten werden kann (EP 0 437 946 B1). Es besteht aber der Nachteil, dass das Verfahren technologisch aufwendig ist, da hohe Anforderungen an die Konstanthaltung der Verdampfungsrate, insbesondere bei Einsatz mehrerer Verdampferschiffchen, gestellt werden müssen.It is also known that the mixing ratio between the evaporated metal and its oxide can be kept substantially uniform by setting a specific reactive gas flow which leads to weakly absorbing layers at a constant evaporation rate (EP 0 437 946 B1). However, there is the disadvantage that the process is technologically complex, since high demands must be made on keeping the evaporation rate constant, in particular when using several evaporation boats.
Es ist weiterhin bekannt, Aluminiumoxidschichten deutlich unterstöchiomethsch aufzudampfen. Die erzielte optische Transmission liegt zunächst unterhalb des oben erwähnten Arbeitsbereiches. In einem Nachoxidationsschritt, der plasmaaktiviert direkt nach der Bedampfung oder ohne Aktivierung bei einem zusätzlichen Umwickeln erfolgt, wird die Schicht nachträglich aufgehellt (EP 0 555 518 Bl , EP 0 695 815 B1). Dieser zusätzliche Prozessschritt bedeutet jedoch einen technologischen Mehraufwand.It is also known to vapor-deposit aluminum oxide layers in a substoichiometric manner. The optical transmission achieved is initially below the working range mentioned above. In a post-oxidation step, which is plasma-activated directly after vapor deposition or without activation with an additional wrapping, the layer is subsequently brightened (EP 0 555 518 B1, EP 0 695 815 B1). However, this additional process step means additional technological effort.
Weiterhin ist bekannt, dass bei der Aufdampfung sehr dünner unterstöchiometrischer Oxidschichten und anschließender relativ langer Verweildauer in der Reaktivgasatmosphäre die Nachoxidation - eventuell plasmaaktiviert - spontan zur ausreichenden Aufhellung der Schicht führt. Durch die Nutzung eines Bandlaufwerkes, welches über zusätzliche Umlenkrollen den Weg des bedampften Substrates im Rezipienten wesentlich verlängert und es daneben gestattet, den Bedampfungszyklus mehrfach zu durchlaufen, können hinreichend transparente Schichten üblicher Dicke aufgedampft werden, indem mehrere sehr dünne und einzeln nachoxidierte Schichten übereinander aufgedampft werden (US 5,462,602). Das Verfahren erfordert jedoch einen erheblichen mechanischen Mehraufwand am Bandlaufwerk.Furthermore, it is known that during the evaporation of very thin, sub-stoichiometric oxide layers and subsequent relatively long residence time in the reactive gas atmosphere, the post-oxidation - possibly plasma-activated - spontaneously leads to sufficient lightening of the layer. By using a tape drive, which significantly extends the path of the vaporized substrate in the recipient via additional deflection rollers and also allows the steaming cycle to be repeated several times, sufficiently transparent layers of conventional thickness can be vapor-deposited by vapor-depositing several very thin and individually reoxidized layers (US 5,462,602). However, the method requires considerable additional mechanical effort on the tape drive.
Es ist bekannt, dass Barriereschichten, welche als Einzelschichten die Mindestanforderungen bezüglich ihrer Barrierewirkung nicht erfüllen, in Mehrschichtsystemen ausreichende Barrierewirkungen zeigen. Die Kombination von aufgestäubten und aufgedampften Schichten ist eine solche Lösung, die auch für Aluminiumoxid vorgeschlagen wurde (DE 43 43 040 C1). Die Beschichtung erfolgt in diesem Fall mit stark unterschiedlicher Beschichtungsrate. Die Realisierung mehrerer aufeinanderfolgender Prozessschritte, die unterschiedliche Durchlaufzeiten bedingen, stellt jedoch ebenfalls einen erheblichen technischen Mehraufwand dar. Außerdem wird die Barrierewirkung derartiger Schichten oft dadurch beschränkt, dass sich in den einzelnen Schichten unterschiedliche Schichtspannungen aufbauen, weshalb es, ausgehend von den Übergangsbereichen, allmählich zu Rissbildungen kommen kann.It is known that barrier layers, which as individual layers do not meet the minimum requirements with regard to their barrier effect, show sufficient barrier effects in multilayer systems. The combination of sputtered and evaporated layers is such a solution that has also been proposed for aluminum oxide (DE 43 43 040 C1). In this case, the coating takes place at a very different coating rate. However, the implementation of several successive process steps, which require different throughput times, also represents a considerable additional technical outlay. In addition, the barrier effect of such layers is often limited by the fact that different layer tensions build up in the individual layers, which is why, starting from the transition areas, it gradually increases Cracks can form.
Weiterhin ist bekannt, dass durch eine Prozessführung, die es verhindert, dass die Dichte der Barriereschicht unter einen bestimmten Grenzwert sinkt, gute Barriereeigenschaften erzielt werden können. So wird für Aluminiumoxid 2,7 g/cm3 als unterer Grenzwert der Dichte beansprucht (EP 0 812 779 A2). Da die Dichte einer Aufdampfschicht jedoch stark von den Kondensationsbedingungen abhängt, stellt ein vorgegebener Mindestwert stets eine deutliche Einschränkung bei der Prozessführung dar. Insbesondere bei der Umrüstung bestehender Aluminiumbedampfungsanlagen für den Prozess der reaktiven Aufdampfung von Aluminiumoxidschichten sind durch konstruktive Gegebenheiten oftmals Kondensationsbedingungen vorgegeben, die nur mit sehr großem Aufwand zu verändern sind und die Umrüstung insgesamt unwirtschaftlich werden lassen. Außerdem ist die Dichte der Schicht kein Parameter, der während des Prozesses direkten Messungen zugänglich ist.It is furthermore known that good process properties that prevent the density of the barrier layer from dropping below a certain limit value can achieve good barrier properties. For aluminum oxide, 2.7 g / cm 3 is claimed as the lower limit of the density (EP 0 812 779 A2). However, since the density of a vapor deposition layer strongly depends on the condensation conditions, a given minimum value always represents a significant limitation in the process control. In particular when converting existing aluminum vapor deposition systems for the process of reactive vapor deposition of aluminum oxide layers, condensation conditions are often specified by design conditions, which are only possible with a great deal of effort has to be changed and the conversion as a whole becomes uneconomical. In addition, the density of the layer is not a parameter that is accessible to direct measurements during the process.
Weiterhin ist bekannt, vor der Beschichtung mit der eigentlichen Barriereschicht das Substrat mit einer dünnen Nukleationsschicht mit einer ungefähren Dicke von 5 nm zu versehen (US 5,792,550). Auch das bedeutet in vielen Fällen einen zusätzlichen Prozessschritt, der die Produktionskosten deutlich erhöht.It is also known to provide the substrate with a thin nucleation layer with an approximate thickness of 5 nm before coating with the actual barrier layer (US Pat. No. 5,792,550). In many cases this also means an additional process step that significantly increases production costs.
Es ist außerdem bekannt, das Substrat mit einem Magnetronplasma zu behandeln, bevor die Beschichtung mit der Barriereschicht erfolgt [Löbig, G. et al.; SVC 41 st Annual Technical Conference Proceedings (1998) S.502]. Das bewirkt eine Aktivierung und Reinigung der Substratoberfläche und sorgt für eine verbesserte Schichthaftung. Dadurch ist die Barrierewirkung etwas weniger abhängig von der Stöchiometrie der Barriereschicht. Für viele Anwendungen reicht die auf diese Weise erzielbare Barriere Wirkung jedoch ebenfalls nicht aus.It is also known to treat the substrate with a magnetron plasma before coating with the barrier layer [Löbig, G. et al .; SVC 41st Annual Technical Conference Proceedings (1998) p.502]. This activates and cleans the Substrate surface and ensures improved layer adhesion. As a result, the barrier effect is somewhat less dependent on the stoichiometry of the barrier layer. However, the barrier effect that can be achieved in this way is also not sufficient for many applications.
Schließlich ist bekannt, die Barriereschicht mit einem Stöchiometriegradienten aufzudampfen (DE 198 45 268 C1 ). In derartigen Schichten stellt jedoch die genaue Einstellung der Stöchiometrie im Grenzbereich zwischen Schicht und Substrat einen sehr sensiblen Parameter dar.Finally, it is known to evaporate the barrier layer with a stoichiometric gradient (DE 198 45 268 C1). In such layers, however, the exact setting of the stoichiometry in the boundary area between the layer and the substrate is a very sensitive parameter.
Aufgabe der Erfindung ist es, ein Verfahren zu schaffen, mit welchem auf bandförmigen Substraten ohne großen technologischen Aufwand transparente Barriereschichten auf Aluminiumoxidbasis durch reaktive Verdampfung hergestellt werden können. Im Falle kleiner Schwankungen der Verdampfungsrate, die sich insbesondere bei Verwendung von Verdampferschiffchen nicht vollkommen ausschließen lassen, soll ohne eine zusätzliche Nachoxidation der durch die geforderten Transmissions- und Barrierewerte bestimmte Arbeitsbereich eingehalten werden. Das Verfahren soll auch durch Nachrüstung bestehender Aluminiumbedampfungsanlagen ausführbar sein.The object of the invention is to provide a method with which transparent barrier layers based on aluminum oxide can be produced by reactive evaporation on tape-shaped substrates without great technological effort. In the event of small fluctuations in the evaporation rate, which cannot be completely ruled out, particularly when using evaporator boats, the work area determined by the required transmission and barrier values should be maintained without additional post-oxidation. The process should also be able to be carried out by retrofitting existing aluminum vapor deposition systems.
Erfindungsgemäß wird die Aufgabe nach Patentanspruch 1 gelöst. Vorteilhafte Ausgestaltungen des Verfahrens sind in den Patentansprüchen 2 bis 18 beschrieben.According to the invention the object is achieved according to claim 1. Advantageous embodiments of the method are described in claims 2 to 18.
Die Erfindung beruht auf der Erkenntnis, dass die Barrierewirkung einer Aluminiumoxidschicht wesentlich weniger stöchiometrieabhängig ist, wenn das Substrat vor der Bedampfung mit der Aluminiumoxidschicht mit einer extrem dünnen aufgestäubten Metalloder Metalloxidschicht versehen wird. Unter extrem dünn wird dabei eine Schichtdicke verstanden, bei der sich noch keine geschlossene Schicht bilden kann. Das ist auf jeden Fall auszuschließen, wenn die Flächenbelegung nicht für Ausbildung einer vollständigen Atomoder Moleküllage reicht, aber auch etwas höhere Flächenbelegungen führen noch nicht zur Ausbildung geschlossener Schichten. Der Aufstäubungsprozess, auch Sputtern genannt, bedingt eine Reinigung und Aktivierung der Substratoberfläche. Das erhöht die Schichthaftung. Die gleichzeitig aufgesputterten Metallatome oder Metalloxidmoleküle weisen außerdem durch die für Sputterprozesse typische Auftreffenergie eine besonders gute Haftung auf, wie sie auch von dickeren gesputterten Schichten bekannt ist. Vorteilhaft ist jedoch, dass sich durch die unvollständige Bedeckung des Substrates mit einer nicht geschlossenen Schicht keinerlei Schichtspannungen aufbauen.The invention is based on the knowledge that the barrier effect of an aluminum oxide layer is significantly less stoichiometry-dependent if the substrate is provided with an extremely thin sputtered metal or metal oxide layer before the aluminum oxide layer is deposited. Extremely thin is understood to mean a layer thickness at which a closed layer cannot yet form. This can be ruled out in any case if the area coverage is not sufficient for the formation of a complete atomic or molecular layer, but somewhat higher area coverage does not yet lead to the formation of closed layers. The sputtering process, also called sputtering, requires cleaning and activation of the substrate surface. This increases shift liability. The metal atoms or metal oxide molecules sputtered on at the same time have particularly good adhesion due to the impact energy typical of sputtering processes, as is also known from thicker sputtered layers. It is advantageous however, that due to the incomplete covering of the substrate with an unclosed layer, no layer tensions build up.
Die nach dem Sputtern noch nicht bedeckten Substratbereiche stehen außerdem aktiviert und gereinigt für die Beschichtung mit der eigentlichen Barriereschicht aus Aluminiumoxid zur Verfügung. Es wurde festgestellt, dass bei einer derartigen Vorbeschichtung die Abhängigkeit der Barrierewirkung von der Schichtstöchiometrie wesentlich schwächer ausgeprägt ist, als ohne diese Vorbeschichtung.The substrate areas not yet covered after sputtering are also activated and cleaned for coating with the actual barrier layer made of aluminum oxide. It was found that the dependence of the barrier effect on the layer stoichiometry is much less pronounced with such a precoating than without this precoating.
Besonders gute Barrierewirkungen lassen sich erreichen, wenn anschließend eine plasmaaktivierte reaktive Bedampfung des vorbeschichteten Substrates mit Aluminiumoxid erfolgt. Zur Plasmaaktivierung eignet sich besonders ein dichtes Hohlkathodenbogenentladungs- plasma. Dessen Wirkung kann durch eine magnetische Verstärkung zusätzlich gesteigert werden. Dies bedingt eine besonders geringe Abhängigkeit der Barrierewirkung von der Schichtstöchiometrie bei konstant guten Barrierewerten. Offenbar bewirkt dieses spezielle Plasma durch seine hohe Ladungsträgerdichte die Ausbildung einer für Barriereschichten optimalen Schichtstruktur. Als vorteilhaft hat sich ein Plasma erwiesen, das am Substrat eine durchschnittliche extrahierbare lonenstromdichte von mindestens 20 mA/cm2 bereitstellt. Besonders vorteilhaft sind lonenstromdichten von über 50 mA/cm2. Eine besonders vorteilhafte Ausführung des erfindungsgemäßen Verfahrens ergibt sich bei Ausnutzung der Tatsache, dass die Barriere gegenüber Sauerstoff nicht in gleicher Weise von der Stöchiometrie abhängt, wie die Barriere gegenüber Wasserdampf. Versuche haben ergeben, dass der Grad, in dem bestimmte Tiefenbereiche der Schicht zur Barrierewirkung der Gesamtschicht beitragen, in unterschiedlichem Maße von der Stöchiometrie abhängt. Wird die optische Transmission der gesamten Schicht entsprechend den späteren anwendungsbedingten Anforderungen konstant gehalten, so kann die Absorption der unterschiedlichen Tiefenbereiche der Schicht durchaus variieren. Eine Schicht mit über die gesamte Schichtdicke gleichmäßig verteilter Stöchiometrie ist nicht von einer Stapelstruktur aus vollständig transparenten und stärker unterstöchiometrischen Teilschichten zu unterscheiden. Gleiches gilt für Schichten, die bezüglich der Stöchiometrie als Gradientenschichten ausgebildet sind. Unterschiedliche Gradienten sind aus der Vermessung der optischen Transmission nicht zu ersehen, solange sich die Absorption der Gesamtschicht nicht ändert.Particularly good barrier effects can be achieved if a plasma-activated reactive vapor deposition of the pre-coated substrate with aluminum oxide then takes place. A dense hollow cathode arc discharge plasma is particularly suitable for plasma activation. Its effect can be further increased by magnetic amplification. This requires a particularly low dependence of the barrier effect on the layer stoichiometry with consistently good barrier values. Apparently, this special plasma, due to its high charge carrier density, leads to the formation of an optimal layer structure for barrier layers. A plasma has proven to be advantageous which provides an average extractable ion current density of at least 20 mA / cm 2 on the substrate. Ion current densities of over 50 mA / cm 2 are particularly advantageous. A particularly advantageous embodiment of the method according to the invention results from the fact that the barrier to oxygen does not depend on the stoichiometry in the same way as the barrier to water vapor. Experiments have shown that the degree to which certain depth regions of the layer contribute to the barrier effect of the overall layer depends to a different degree on the stoichiometry. If the optical transmission of the entire layer is kept constant in accordance with the later application-related requirements, the absorption of the different depth ranges of the layer can certainly vary. A layer with stoichiometry evenly distributed over the entire layer thickness cannot be distinguished from a stack structure of completely transparent and more sub-stoichiometric partial layers. The same applies to layers which are designed as gradient layers with respect to the stoichiometry. Different gradients cannot be seen from the measurement of the optical transmission as long as the absorption of the entire layer does not change.
Liegt nun ein überstöchiometrischer Bereich in der Nähe des Substrates, ergeben sich schlechte Barrierewerte gegenüber Wasserdampf und mäßige Werte gegenüber Sauerstoff. Enthält der untere Teil der Schicht dagegen einen unterstöchiometrischen Bereich, lassen sich gute Wasserdampf- und Sauerstoffbarrierewerte erzielen. Es sind also erfindungsgemäß unterstöchiometrische Bereiche im substratnahen unteren Teil der Schicht anzustreben. Die anderen Bereiche der Schicht können durchaus überstöchio- metrisch sein. Diese Bereiche tragen immerhin noch zur Sauerstoffbarriere bei, haben jedoch auf die Wasserdampfbarriere kaum einen Einfluss. Es lässt sich ableiten, dass diese Bereiche auch von geringerer Dichte sein werden, weshalb der Dichte der Gesamtschicht kaum eine Bedeutung zukommt.If there is a superstoichiometric range in the vicinity of the substrate, there are poor barrier values against water vapor and moderate values against oxygen. In contrast, if the lower part of the layer contains a substoichiometric range, good water vapor and oxygen barrier values can be achieved. According to the invention, sub-stoichiometric regions in the lower part of the layer close to the substrate should therefore be aimed for. The other areas of the layer can be overstoichiometric. These areas still contribute to the oxygen barrier, but have hardly any influence on the water vapor barrier. It can be deduced that these areas will also be of lower density, which is why the density of the overall layer is of little importance.
Durch reaktive Aluminiumverdampfung in Kombination mit der Aktivierung durch ein Hohlkathodenbogenentladungsplasma und einem erfindungsgemäßen Vorsputtern, beispielsweise mit Titan oder Magnesium oder reaktiv mit deren Oxid, lassen sich Barriere- schichten mit exzellenter Barrierewirkung erzeugen. Besonders vorteilhaft ist dabei, dass sich beide Beschichtungsschritte mit der gleichen Durchlaufzeit des Substrates realisieren lassen, da sich die Beschichtungsraten in einem ähnlichen Verhältnis zueinander bewegen wie die Flächenbelegungen durch die nicht geschlossene Sputterschicht und die eigentliche Barriereschicht. Somit kann die Beschichtung in einem einzigen Durchlauf erfolgen.Through reactive aluminum evaporation in combination with the activation by a hollow cathode arc discharge plasma and a pre-sputtering according to the invention, for example with titanium or magnesium or reactive with their oxide, barrier layers with an excellent barrier effect can be produced. It is particularly advantageous that both coating steps can be carried out with the same throughput time of the substrate, since the coating rates move in a similar relationship to one another as the area occupancies through the non-closed sputter layer and the actual barrier layer. Coating can thus be carried out in a single pass.
Das erfindungsgemäße Verfahren besteht in der Vorbeschichtung des Substrates durch reaktives oder nichtreaktives Sputtern mit einer nicht geschlossenen Schicht aus einem Metall oder dessen Oxid und einer anschließenden reaktiven Verdampfung von Aluminium aus einem Schiffchenverdampfer, einem Induktionsverdampfer oder einem Elektronen- Strahlverdampfer. Vorteilhafterweise wird der Schritt der reaktiven Bedampfung durch eine Plasmaaktivierung ergänzt und das Reaktivgas in einer Weise eingelassen, dass sich entlang der Bedampfungszone in Bandlaufrichtung ein geeigneter Partialdruckgradient des Reaktivgases einstellt. Mit dem erfindungsgemäßen Verfahren lassen sich so Aluminiumoxidschichten auf band- förmige Substrate aufdampfen, die bezüglich ihrer Stöchiometrie bzw. des Mischungsverhältnisses zwischen dem verdampften Metall und seinem Oxid als Gradientenschichten oder als Stapelschichten ausgebildet sind und deren unterstöchiometrischster Bereich im substratnahen Teil der Schicht liegt. Gradientenschichten haben in diesem Falle gegenüber Stapelstrukturen den Vorteil, dass sie sich in einem Verfahrensschritt aufdampfen lassen.The method according to the invention consists in the precoating of the substrate by reactive or non-reactive sputtering with a non-closed layer made of a metal or its oxide and a subsequent reactive evaporation of aluminum from a boat evaporator, an induction evaporator or an electron beam evaporator. The step of reactive vapor deposition is advantageously supplemented by plasma activation and the reactive gas is let in in such a way that a suitable partial pressure gradient of the reactive gas is established along the vapor deposition zone in the direction of strip travel. With the method according to the invention, aluminum oxide layers can thus be vapor-deposited onto band-shaped substrates which, with regard to their stoichiometry or the mixing ratio between the evaporated metal and its oxide, are designed as gradient layers or as stacked layers and whose most sub-stoichiometric region lies in the part of the layer close to the substrate. In this case, gradient layers have the advantage over stacked structures that they can be vapor-deposited in one process step.
Der im sichtbaren Bereich absorbierende Tiefenbereich der Schicht kann sehr dünn, d. h. bei <10 nm gehalten werden. Da an so dünnen Schichten Schwankungen im Grad der Unter- stöchiometrie erst bei deutlichen Abweichungen sichtbar werden, und Veränderungen in überstöchiometrischen Bereichen - solange sie nur überstöchiometrisch oder zumindest stöchiometrisch bleiben - keinen Einfluss auf die Absorption der Gesamtschicht haben, sind die Anforderungen an die Einhaltung einer gerade noch tolerablen Absorption wesentlich unkritischer, als das bei Schichten mit im Wesentlichen gleichmäßiger Stöchiometrie der Fall ist.The depth range of the layer absorbing in the visible range can be kept very thin, ie at <10 nm. Since fluctuations in the degree of sub-stoichiometry on such thin layers only become apparent when there are clear deviations, and changes in super-stoichiometric areas - as long as they remain super-stoichiometric or at least stoichiometric - have no influence on the absorption of the overall layer the requirements for maintaining a just tolerable absorption are much less critical than is the case with layers with essentially uniform stoichiometry.
Die reaktive Verdampfung kann auch für den Fall der Ausbildung von Gradientenschichten plasmaaktiviert erfolgen, was die Barriereeigenschaften des Endproduktes weiter verbessert. Der wesentliche Vorteil des Verfahrens unter Einbeziehung von Gradientenschichten besteht in der extrem geringen Dicke der unterstöchiometrischen Schicht, wodurch erst bei sehr niedrigem Oxidationsgrad ein nennenswerter Transmissionsverlust eintritt. Dadurch wird in den meisten Fällen ein zusätzlicher Nachoxidationsschritt überflüssig. Alle anderen Schichtbereiche sind ohnehin transparent. Das Verfahren zielt in diesem Fall also nicht auf die Erreichung einer möglichst schwachen, aber sehr gleichmäßigen Unterstöchiometrie, sondern auf die Erzeugung einer Gradientenschicht, die in ihrem unteren Bereich eine sehr dünne, aber durchaus stärker unterstöchiometrische Zone aufweist. Die Gleichmäßigkeits- anforderung in Bezug auf die optische Transmission ist dadurch wesentlich einfacher zu erfüllen. Der erfindungsgemäße Einsatz des Hohlkathodenbogenentladungsplasmas sorgt zusätzlich für eine Verringerung der Abhängigkeit der Barriereeigenschaften von der Stöchiometrie der Oxidschicht und erweitert damit den zur Verfügung stehenden Arbeitsbereich. Eine besonders hohe Prozesssicherheit ergibt sich, wenn Prozessparameter geregelt werden. Besonders vorteilhaft ist es, wenn die jeweiligen Prozessparameter für einzelne Sektoren des Bedampfungsbereiches separat geregelt werden. Dafür eignen sich als zu regelnde Prozessparameter die pro Zeiteinheit verdampfte Aluminiummenge und/oder der Reaktivgasfluss. Besonders vorteilhaft ist es, wenn die Regelung eine transmissionsgesteuerte Regelung der Sauerstoffzufuhr ist, bei der die Sauerstoffzufuhr so eingestellt wird, dass die optische Transmission, welche während des Prozesses kontinuierlich oder periodisch gemessen wird, auf einem Sollwert gehalten wird.The reactive evaporation can also be plasma-activated in the case of the formation of gradient layers, which further improves the barrier properties of the end product. The main advantage of the method, including gradient layers, is the extremely small thickness of the substoichiometric layer, which means that a significant transmission loss only occurs when the degree of oxidation is very low. In most cases, this means that an additional post-oxidation step is unnecessary. All other layer areas are transparent anyway. In this case, the method therefore does not aim to achieve the weakest but very uniform sub-stoichiometry, but rather the creation of a gradient layer which has a very thin but definitely more sub-stoichiometric zone in its lower region. This makes it much easier to meet the uniformity requirement with regard to optical transmission. The use of the hollow cathode arc discharge plasma according to the invention additionally reduces the dependency of the barrier properties on the stoichiometry of the oxide layer and thus expands the available work area. Process reliability is particularly high if process parameters are regulated. It is particularly advantageous if the respective process parameters are regulated separately for individual sectors of the vapor deposition area. Suitable process parameters to be controlled are the amount of aluminum evaporated per unit of time and / or the reactive gas flow. It is particularly advantageous if the regulation is a transmission-controlled regulation of the oxygen supply, in which the oxygen supply is adjusted in such a way that the optical transmission, which is measured continuously or periodically during the process, is kept at a desired value.
Eine besonders vorteilhafte Ausgestaltung des Verfahrens besteht darin, zur Begrenzung des Bedampfungsbereiches eine bewegliche Blende anzuordnen. Damit lassen sich für den Fall, dass sich aus konstruktiven Gründen - z. B. im unteren Teil der Schicht - überstöchio- metrische Bereiche nicht vermeiden lassen, diese ausblenden.A particularly advantageous embodiment of the method consists in arranging a movable diaphragm to limit the vaporization area. This means that in the event that for structural reasons - e.g. B. in the lower part of the layer - do not let superstoichiometric areas be avoided, hide them.
Anhand eines Ausführungsbeispieles wird die Erfindung näher beschrieben. In einer an sich bekannten Bandbedampfungsanlage, bestehend aus einem Rezipienten mit angeschlossenem Vakuumpumpsystem und Bandwickeleinrichtung, wird das zu bedampfende Substrat - in diesem Fall eine PET-Folie - an einer mit Titantargets belegten Magnetronquelle vorbeigeführt, die unter Einlass von Argon und Sauerstoff als Sputterquelle dient. Als Magnetronquelle werden Einzel- oder Doppelanordnungen von Magnetrons verwendet. Die eingespeiste Leistung wird so eingestellt, dass sich auf dem Substrat eine nicht geschlossene Schicht bildet. Die Flächenbelegung liegt dabei unter einer effektiven Schichtdicke von einem Nanometer. Die optimale Sputterleistung hängt von der realisierten Bandgeschwindigkeit ab. So haben sich bei Bandgeschwindigkeiten um 5 m/s Leistungsdichten bis 15 W/cm2 Targetfläche bewährt. Anschließend wird das Substrat über eine Kühlwalze geführt. Darunter befindet sich in Verdampferschiffchen das Verdampfungsgut, welches den Verdampferschiffchen in bekannter Weise kontinuierlich zugeführt wird und auf das Substrat aufgedampft wird. Das Verdampferschiffchen wird mit konstanter Verdampfungsrate betrieben. Der wirksame Bedampfungsbereich ist mittels einer beweglichen Blende einstellbar. Seitlich vom Bedampfungsbereich zwischen der Kühlwalze und dem Verdampferschiffchen sind Gaseinlassdüsen für die Zuführung des Reaktivgases Sauerstoff angeordnet. Die Positionen der Gaseinlassdüsen sowie deren Winkel sind in Pfeilrichtung einstellbar. Der Reaktivgasfluss durch die Gaseinlassdüsen in der Nähe der Bandeinlaufzone ist manuell einstellbar. Der Reaktivgasfluss durch die anderen Gaseinlass- düsen erfolgt transmissionsgeregelt. Die dafür erforderliche Messung der optischen Transmission erfolgt mittels bekannter Messeinrichtungen außerhalb der Bedampfungszone, jedoch vor Erreichen des Aufwickels.The invention is described in more detail using an exemplary embodiment. In a tape evaporation system known per se, consisting of a recipient with a connected vacuum pump system and tape winding device, the substrate to be vaporized - in this case a PET film - is guided past a magnetron source covered with titanium targets, which serves as a sputtering source while admitting argon and oxygen. Single or double arrangements of magnetrons are used as the magnetron source. The power fed in is adjusted in such a way that an unclosed layer forms on the substrate. The area coverage is less than an effective layer thickness of one nanometer. The optimal sputtering performance depends on the realized belt speed. For example, at belt speeds of 5 m / s power densities up to 15 W / cm 2 target area have proven their worth. The substrate is then passed over a chill roll. Below this is the evaporation material in evaporator boats, which is continuously fed to the evaporator boats in a known manner and is evaporated onto the substrate. The evaporator boat is operated at a constant evaporation rate. The effective steaming range can be set using a movable screen. Gas inlet nozzles for supplying the reactive gas oxygen are arranged to the side of the vaporization area between the cooling roller and the evaporator boat. The positions of the gas inlet nozzles and their angles can be adjusted in the direction of the arrow. The reactive gas flow through the gas inlet nozzles near the strip inlet zone can be adjusted manually. The reactive gas flow through the other gas inlet nozzles is transmission-controlled. The measurement of the optical transmission required for this is carried out by means of known measuring devices outside the vapor deposition zone, but before reaching the winding.
Das erfindungsgemäße Verfahren wird im Falle der Ausbildung einer Schicht mit einem Stöchiometriegradienten wie folgt ausgeführt:In the case of the formation of a layer with a stoichiometric gradient, the method according to the invention is carried out as follows:
Die Inbetriebnahme der Aluminiumverdampfung erfolgt in bekannter Weise. Danach wird der Reaktivgasfluss an den Gaseinlassdüsen in der Nähe der Bandeinlaufzone auf 0 bis 40 % der entsprechend der chemischen Reaktionsgleichung für eine vollständige Oxidation der gesamten Schicht erforderlichen Menge Sauerstoff eingestellt. Im Anschluss daran werden die geregelten Gaseinlassdüsen auf der Bandauslaufseite unter Vorgabe des gewünschten Sollwertes der optischen Transmission von 80 bis 95 % geöffnet, worauf sich der noch benötigte Reaktivgasfluss automatisch einstellt. Bei Beginn des Verfahrens oder nach Veränderungen der Positionen der Gaseinlassdüsen oder Blenden ist der einzustellende Reaktivgasfluss an den Gaseinlassdüsen wie folgt zu ermitteln:The aluminum evaporation is started up in a known manner. The reactive gas flow at the gas inlet nozzles in the vicinity of the strip inlet zone is then adjusted to 0 to 40% of the amount of oxygen required for a complete oxidation of the entire layer in accordance with the chemical reaction equation. The regulated gas inlet nozzles on the strip outlet side are then opened, specifying the desired setpoint for the optical transmission of 80 to 95%, whereupon the reactive gas flow that is still required is automatically set. At the start of the process or after changing the positions of the gas inlet nozzles or orifices, the reactive gas flow to be set at the gas inlet nozzles must be determined as follows:
Das Substrat wird bei verschiedenen Einstellungen des Reaktivgasflusses an den Gaseinlassdüsen bedampft. Danach erfolgt die Vermessung der bedampften Substrate bezüglich ihrer Permeationswerte für Wasserdampf und/oder Sauerstoff. Anschließend wird an den Gaseinlassdüsen der Reaktivgasfluss, bei welchem sich der niedrigste Permeationswert für Wasserdampf und/oder Sauerstoff ergab, eingestellt. The substrate is vapor-deposited at various settings of the reactive gas flow at the gas inlet nozzles. The vaporized substrates are then measured for their permeation values for water vapor and / or oxygen. The reactive gas flow, at which the lowest permeation value for water vapor and / or oxygen resulted, is then set at the gas inlet nozzles.

Claims

Patentansprüche claims
1. Verfahren zum Bedampfen bandförmiger Substrate mit einer transparenten Barriereschicht aus Aluminiumoxid durch reaktive Verdampfung von Aluminium und Einlass von Reaktivgas in einer Bandbedampfungsanlage, dadurch gekennzeichnet, dass vor der Beschichtung mit Aluminiumoxid eine unvollständig geschlossene Schicht aus einem Metall oder einem Metalloxid durch Magnetronsputtern auf das Substrat aufgebracht wird.1. A method for vapor deposition of strip-shaped substrates with a transparent barrier layer made of aluminum oxide by reactive evaporation of aluminum and inlet of reactive gas in a strip vapor deposition system, characterized in that before coating with aluminum oxide, an incompletely closed layer of a metal or a metal oxide by magnetron sputtering onto the substrate is applied.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die Flächenbelegung durch die unvollständig geschlossene Schicht einer Schichtdicke von weniger als einem Nanometer entspricht.2. The method according to claim 1, characterized in that the area occupied by the incompletely closed layer corresponds to a layer thickness of less than one nanometer.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass zur Bildung der unvollständig geschlossenen Schicht Titan oder Magnesium gesputtert wird.3. The method according to claim 1 or 2, characterized in that titanium or magnesium is sputtered to form the incompletely closed layer.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass das Sputtern reaktiv unter Sauerstoffeinlass erfolgt.4. The method according to claim 3, characterized in that the sputtering is carried out reactively with oxygen admission.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Einlass des Reaktivgases derart erfolgt, dass sich in der Bedampfungszone in Bandlaufrichtung ein Partialdruckgradient des Reaktivgases einstellt, dass sich das Mischungsverhältnis zwischen Aluminium, Aluminiumoxid und Sauerstoff in der Barriereschicht als Gradient ausbildet, dass dieses Mischungsverhältnis in der Barriereschicht ein Maximum des Anteils des metallischen Aluminiums aufweist und die Lage und Ausprägung dieses Maximums in einem bestimmten Tiefenbereich der Barriereschicht durch Variation des Partialdruck- gradienten des Reaktivgases und der Lage der Bedampfungszone derart eingestellt wird, dass bei gleicher optischer Transmission der Barriereschicht die Sauerstoff- permeation und/oder die Wasserdampfpermeation ein Minimum erreicht.5. The method according to any one of claims 1 to 4, characterized in that the inlet of the reactive gas takes place in such a way that a partial pressure gradient of the reactive gas is established in the vapor deposition zone in the direction of strip travel that the mixture ratio between aluminum, aluminum oxide and oxygen in the barrier layer is a gradient Forms that this mixture ratio in the barrier layer has a maximum of the proportion of metallic aluminum and the position and expression of this maximum in a certain depth range of the barrier layer is adjusted by varying the partial pressure gradient of the reactive gas and the position of the vaporization zone in such a way that with the same optical Transmission of the barrier layer reaches a minimum the oxygen permeation and / or the water vapor permeation.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass die Lage und Ausprägung des Maximums an metallischem Aluminium in einem bestimmten Tiefenbereich der Barriereschicht durch Verstellen von Blenden im Verdampfungsbereich und/oder Veränderung der Position des Verdampferschiffchens und/oder Verände- rung der Position der Gaseinlassdüse und/oder des Winkels der Gaseinlassdüsen für das Reaktivgas und/oder die Veränderung der Reaktivgasflüsse eingestellt wird.6. The method according to claim 5, characterized in that the position and expression of the maximum of metallic aluminum in a certain depth region of the barrier layer by adjusting orifices in the evaporation region and / or changing the position of the evaporator boat and / or changes. tion of the position of the gas inlet nozzle and / or the angle of the gas inlet nozzles for the reactive gas and / or the change in the reactive gas flows is set.
7. Verfahren nach einem der Ansprüche 5 oder 6, dadurch gekennzeichnet, dass das Aluminium aus einem Schiffchenverdampfer mit mindestens einem Verdampferschiffchen mit kontinuierlicher Drahtzufuhr verdampft wird.7. The method according to any one of claims 5 or 6, characterized in that the aluminum is evaporated from a boat evaporator with at least one evaporator boat with continuous wire feed.
8. Verfahren nach einem der Ansprüche 5 oder 6, dadurch gekennzeichnet, dass das Aluminium aus einem Induktionsverdampfer verdampft wird.8. The method according to any one of claims 5 or 6, characterized in that the aluminum is evaporated from an induction evaporator.
9. Verfahren nach einem der Ansprüche 5 oder 6, dadurch gekennzeichnet, dass das Aluminium aus einem Elektronenstrahlverdampfer verdampft wird.9. The method according to any one of claims 5 or 6, characterized in that the aluminum is evaporated from an electron beam evaporator.
10. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass der Partialdruck- gradient des Reaktivgases durch Variation des Verhältnisses der Reaktivgasflüsse der im Bereich der Bandeinlaufzone und Bandauslaufzone angeordneten, separat einstellbaren Gaseinlassdüsen eingestellt wird.10. The method according to claim 6, characterized in that the partial pressure gradient of the reactive gas is adjusted by varying the ratio of the reactive gas flows of the separately adjustable gas inlet nozzles arranged in the area of the strip inlet zone and strip outlet zone.
1 1. Verfahren nach mindestens einem der Ansprüche 1 bis 10, dadurch gekenn- zeichnet, dass Prozessparameter geregelt werden.1 1. The method according to at least one of claims 1 to 10, characterized in that process parameters are regulated.
12. Verfahren nach Anspruch 1 1 , dadurch gekennzeichnet, dass die Prozessparameter für einzelne Sektoren des Bedampfungsbereiches separat geregelt werden.12. The method according to claim 1 1, characterized in that the process parameters for individual sectors of the vapor deposition area are controlled separately.
13. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, dass die zu regelnden Prozessparameter die pro Zeiteinheit verdampfte Aluminiummenge und/oder der Reaktivgasfluss sind.13. The method according to claim 11 or 12, characterized in that the process parameters to be controlled are the amount of aluminum evaporated per unit time and / or the reactive gas flow.
14. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, dass die Regelung eine transmissionsgesteuerte Regelung der Sauerstoffzufuhr ist, bei der die14. The method according to claim 11 or 12, characterized in that the regulation is a transmission-controlled regulation of the oxygen supply, in which the
Sauerstoffzufuhr so eingestellt wird, dass die optische Transmission, welche während des Prozesses kontinuierlich oder periodisch gemessen wird, auf einem Sollwert gehalten wird. Oxygen supply is adjusted so that the optical transmission, which is measured continuously or periodically during the process, is kept at a desired value.
15. Verfahren nach mindestens einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass plasmaaktiviert bedampft wird.15. The method according to at least one of claims 1 to 14, characterized in that vapor-activated is vapor-deposited.
16. Verfahren nach Anspruch 15, dadurch gekennzeichnet, dass zur Plasmaaktivierung ein Hohlkathodenbogenentladungsplasma eingesetzt wird.16. The method according to claim 15, characterized in that a hollow cathode arc discharge plasma is used for plasma activation.
17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, dass die Plasmaquellen so betrieben werden, dass sich am Substrat eine durchschnittliche lonenstromdichte von mindestens 20 mA/cm2 extrahieren lässt.17. The method according to claim 16, characterized in that the plasma sources are operated such that an average ion current density of at least 20 mA / cm 2 can be extracted from the substrate.
18. Verfahren nach Anspruch 16, dadurch gekennzeichnet, dass die Plasmaquellen so betrieben werden, dass sich am Substrat eine durchschnittliche lonenstromdichte von mindestens 50 mA/cm2 extrahieren lässt. 18. The method according to claim 16, characterized in that the plasma sources are operated so that an average ion current density of at least 50 mA / cm 2 can be extracted from the substrate.
EP03757995A 2002-11-29 2003-10-16 Method for vapor-depositing strip-shaped substrates with a transparent barrier layer made of aluminum oxide Expired - Lifetime EP1565591B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10255822A DE10255822B4 (en) 2002-11-29 2002-11-29 Process for the vapor deposition of ribbon-shaped substrates with a transparent barrier layer made of aluminum oxide
DE10255822 2002-11-29
PCT/EP2003/011477 WO2004050945A2 (en) 2002-11-29 2003-10-16 Method for vapor-depositing strip-shaped substrates with a transparent barrier layer made of aluminum oxide

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DE (2) DE10255822B4 (en)
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MX (1) MXPA05005113A (en)
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ATE375409T1 (en) 2007-10-15
US20060257585A1 (en) 2006-11-16
DE10255822A1 (en) 2004-06-17
AU2003274021A8 (en) 2004-06-23
RU2352683C2 (en) 2009-04-20
WO2004050945A3 (en) 2004-08-12
US7541070B2 (en) 2009-06-02
CR7821A (en) 2005-11-15
CA2505027A1 (en) 2004-06-17
DE10255822B4 (en) 2004-10-28
AU2003274021A1 (en) 2004-06-23
ECSP055797A (en) 2005-08-11
BR0315699B1 (en) 2012-11-27
ES2290496T3 (en) 2008-02-16
EP1565591B1 (en) 2007-10-10
WO2004050945A2 (en) 2004-06-17
RU2005116674A (en) 2007-01-10
DE50308370D1 (en) 2007-11-22
CO5690658A2 (en) 2006-10-31
MXPA05005113A (en) 2008-03-11
CA2505027C (en) 2011-02-22
BR0315699A (en) 2005-09-06

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